Organic carrier supported metallocene catalyst for olefin polymerization

ABSTRACT

The organic carrier supported metallocene catalyst of the present invention is prepared by preparing a ligand complex of a silicone compound having at least one halogen, an alkyl group and a cycloalkane dienyl group, activating styrene polymer or styrene/divinylbenzene copolymer with a strong base including a metal atom such as Li, Na, K or Mg, reacting the activated polymer or copolymer with the ligand complex of a silicone compound so that the ligand may be supported on the activated polymer or copolymer, and reacting the organic carrier supported ligand with a compound of a transition metal of Group IVb of the Periodic Table or Lanthanides of Atomic Number 58-71. The styrene polymer or styrene/divinylbenzene copolymer may be alkylated by Friedel-Crafts alkylation before they are activated with a strong base.

This application is a division of application Ser. No. 08/585,694, filedJan. 16, 1996, now U.S. Pat. No. 5,610,115.

FIELD OF THE INVENTION

The present invention relates to metallocene catalysts for olefinpolymerization which are supported on an organic carrier. Moreparticularly, the present invention relates to metallocene catalysts forpolymerizing or copolymerizing olefins such as α-olefins, cycloolefinsand dienvinyl monomers, which are supported on a styrene/divinyl benzenecopolymer as a carrier.

The present invention includes a process for preparing the metallocenecatalysts supported on a styrene/divinylbenzene copolymer and a processfor polymerizing or copolymerizing olefins using the metallocenecatalysts.

BACKGROUND OF THE INVENTION

The polymerization of olefins is well known and has been a widelypracticed commercial art for many decades. Catalysts for suchpolymerization are well known to include Ziegler-Natta type catalysts.In the Ziegler-Natta type catalyst field, the catalyst is usually madeup of a transition metal compound such as titanium tetrachloride and analkyl aluminum as a co-catalyst such as trimethyl or triethyl aluminum

However, in order to improve physical properties of polymers of olefins,various researches and developments on catalysts having a highpolymerization activity have been carried out. In this regard,metallocene catalysts have been developed, which are superior inpolymerization activity and stereoregularity to Ziegler-Natta typecatalysts.

U.S. Pat. No. 4,808,561 to Welborn, Jr. discloses an olefinpolymerization catalyst comprising the supported reaction product of atleast one metallocene of a metal of Group IVb of the Periodic Table andan aluminoxane. The reaction product is formed in the presence of thesupport which is a porous inorganic metal oxide of Group 2a, 3a, 4a or4b metal.

U.S. Pat. No. 4,921,825 to Kioka et al. discloses a process forpreparing a solid catalyst for olefin polymerization from analuminoxane, a compound of a transition metal of Group IVb of thePeriodic Table and a certain organic or inorganic compound carrier,which comprises contacting a solution of said aluminoxane in a firstsolvent with a second solvent in which the aluminoxane is insoluble, inthe presence of said certain organic or inorganic compound carrier, todeposit said aluminoxane on said certain organic or inorganic compoundcarrier.

U.S. Pat. No. 5,122,491 discloses a catalyst useful for thepolymerization of an olefin prepared from (A) a compound selected fromthe group consisting of zirconium and hafnium compounds having a ligandincluding conjugated π electron, (B) an aluminoxane, and (C) anorganoaluminum compound.

U.S. Pat. No. 5,362,824 discloses a polymerization catalyst comprisingat least one metallocene and at least one aluminoxane dispersed on thesurface of a resinous substrate comprising a cross-linked copolymer ofabout 30% divinyl benzene, about 55% styrene, and about 15% of acetoxyor hydroxy styrene.

Typically, homogeneous metallocene catalysts are capable of producing anolefin polymer having a narrow molecular-weight distribution and astereoregularity. However, the homogeneous metallocene catalysts aredisadvantageous in polymer morphology, shape and size of polymerparticle, and bulk density. Accordingly, intensive researches arefocused on heterogeneous metallocene catalysts for olefinpolymerization. Some heterogeneous metallocene catalysts supported on aninorganic carrier such as SiO₂, Al₂ O₃ or MgCl₂ have already beendeveloped. In particular, the heterogeneous metallocene catalysts canprepare a polypropylene having high stereoregularity.

In order to provide a metallocene catalyst for preparing an olefinpolymer having improved properties, the present inventors have developeda new process for preparing an organic carrier supported metallocenecatalyst useful for polymerization of olefins.

OBJECTS OF THE INVENTION

An object of this invention is to provide an organic carrier supportedmetallocene catalyst for olefin polymerization.

Another object of the invention is to provide a new process forpreparing an organic carrier supported metallocene catalyst for olefinpolymerization

A further object of the invention is to provide an organic carriersupported metallocene catalyst with a good activity for olefinpolymerization and a process thereof.

A further object of the invention is to provide a process for preparingolefin polymers with a good molecular-weight distribution, high meltingtemperature and high stereoregularity using an organic carrier supportedmetallocene catalyst of this invention

There and other objects and advantages may be found in variousembodiments of the present invention. It is not necessary that each andevery object or advantage be found in all embodiments of the presentinvention. It is sufficient that the present invention may beadvantageously employed.

Other objects and advantages of this invention will be apparent from theensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

The organic carrier supported metallocene catalyst according to thepresent invention is prepared by preparing a ligand complex forsupporting on an organic carrier, activating an organic carrier throughionization with a strong base, reacting the activated organic carrierwith the ligand complex, and reacting the resulting product with a metalcompound.

More particularly, the organic carrier supported metallocene catalyst ofthe present invention is prepared by preparing a ligand complex of asilicon compound having at least one halogen, an alkyl group and acycloalkane dienyl group, activating styrene polymer orstyrene/divinylbenzene copolymer with a strong base including a metalatom such as Li, Na, K or Mg, reacting the activated polymer orcopolymer with the ligand complex of a silicon compound so that theligand may be supported on the activated polymer or copolymer, andreacting the organic carrier supported ligand with a compound of atransition metal of Group IVb of the Periodic Table or Lanthanides ofAtomic Number 58-71. The styrene polymer or styrene/divinylbenzenecopolymer may be alkylated by Friedel-Crafts alkylation before they areactivated with a strong base.

In the process for preparing the organic carrier supported metallocenecatalyst, an alkylene bonded cycloalkanediene can be used as a ligandcomplex substituting a silicon compound. In this case, the styrenepolymer or styrene/divinylbenzene copolymer is activated with ahalogenated alkyl ether.

DETAILED DESCRIPTION OF THE INVENTION

The organic carrier supported metallocene catalyst according to thepresent invention is prepared in the following manner.

First, a ligand complex for supporting on an organic carrier isprepared. An exemplary ligand complex is a silicon compound having atleast one halogen, an alkyl group and a cycloalkane dienyl group,represented by the general formula(I): ##STR1##

wherein A is a halogen or a lower alkyl of C₁ -C₆, X is halogen, a loweralkoxy of C₁ -C₆ or a phenoxy, and M and N are selected from the groupconsisting of cyclopentadienyl, indenyl, fluorenyl, alkyl-substitutedindenyl, and alkyl-substituted fluorenyl, and can be the same ordifferent from each other.

The ligand complex may be prepared by reacting a silicon compound havinghalogen and/or alkyl group with a cycloalkanediene. The ligand complexcan be easily prepared by those skilled in the art.

Exemplary cycloalkanedienes for preparing the ligand complex arecyclopentadiene, indene and fluorene. Exemplary silicon compounds forpreparing the ligand complex are tetrachlorosilane and1-methyltrichlorosilane.

In order to prepare the ligand complex of general formula(I), acycloalkanediene is reacted in a solvent with an organometal compound soas to make the cycloalkanediene be in a salt state, then to theresultant is added a silicon compound.

In the present invention, an organic carrier is employed to support aligand complex. In order for a ligand complex to be supported on anorganic carrier, the organic carrier is activated through ionizationwith strong base. The exemplary organic carriers useful in thisinvention are styrene polymer and styrene/divinylbenzene copolymer.Preferable, styrene/divinylbenzene copolymer containing 2 to 5% byweight of divinylbenzene may be used as organic carrier. The strong baseincludes a metal atom of Li, Na, K or Mg. The activation of an organiccarrier with a strong base is carried out by ionization of the organiccarrier with an organometal compound and other additives. By activation,the organic carrier becomes an polymer-metal salt state.

As an embodiment of this invention, the styrene polymer andstyrene/divinylbenzene copolymer may be alkylated by Friedel-Craftsalkylation before they are activated with a strong base. In thisembodiment, the benzene ring of the styrene polymer or styrene/divinylbenzene copolymer is alkylated by Friedel-Crafts alkylation.

An organic carrier supported ligand complex is prepared by reacting theactivated styrene polymer or styrene/divinylbenzene copolymer with theligand complex of a silicon compound, wherein a ligand is supported onan organic carrier first.

Then, the organic carrier supported ligand complex is reacted with acompound of a transition metal of Group IVb of the Periodic Table orLanthanides of Atomic Number 58-71, finally providing an organic carriersupported metallocene catalyst according to the present invention.

In case of A and X in general formula(I) being halogens, a metallocenecatalyst represented by following formula(II a) may be obtained. In caseof A being a lower alkyl of C₁ -C₆, a metallocene catalyst representedby formula(II b) may be obtained. And, in case of A being a lower alkylof C₁ -C₆ and an organic carrier being alkylated by Friedel-Craftsalkylation, a metallocene catalyst of formula(II c) may be obtained:##STR2##

wherein R₁ and R₂ are an alkyl of C₁ -C₆ and are the same or differentfrom each other, M and N are a cyclopentadienyl, an indenyl, afluorenyl, an alkyl-substituted indenyl or an alkyl-substitutedfluorenyl and are the same or different from each other, Me is atransition metal of Group IVb or Lanthanides, and Y is a halogen, alower alkyl of C₁ -C₆ or a phenoxy.

In a preferable metallocene catalyst represented by formula(II a), Me iszirconium, M and N are all indenyl, and Y is chlorine.

In a preferable metallocene catalyst represented by formula(II b), Me iszirconium, M and N are all indenyl, R₁ is methyl, and Y is chlorine.

In a preferable metallocene catalyst represented by formula(II c), Me iszirconium, M and N are all indenyl, R₁ is methyl, R₂ is isopropyl, and Yis chlorine.

As another type of a ligand complex in accordance with the presentinvention, an alkylene bonded cycloalkanediene can be employedsubstituting a silicone compound, which is represented by the followinggeneral formula(III): ##STR3##

wherein M and N are selected from the group consisting ofcyclopentadienyl, indenyl, fluorenyl, alkyl-substituted indenyl andalkyl-substituted fluorenyl, and can be the same or different from eachother, and n is an integer of 2-4.

In the process using an alkylene bonded cycloalkanediene as ligandcomplex, the organic carrier is activated with a halogenated alkyl etherthrough alkylation. Exemplary alkylene bonded cycloalkanediene ischloroethylmethylether.

The activated organic carrier is reacted with the alkylene bondedcycloalkanediene so that the ligand may be supported on the carrier.Then, the organic carrier supported ligand is reacted with a compound ofa transition metal of Group IVb of the Periodic Table or Lanthanides ofAtomic Number 58-71, finally providing an organic carrier supportedmetallocene catalyst represented by the following general formula(IV):##STR4##

wherein M and N are selected from the group consisting ofcyclopentadienyl, indenyl, fluorenyl, alkyl-substituted indenyl andalkyl-substituted fluorenyl, and can be the same or different from eachother, Me is a transition metal of Group IVb or Lanthanides, Y is ahalogen, a lower alkyl of C₁ -C₆ or a phenoxy, m is an integer of 1-3, nis an integer of 2-4, and n' is an integer.

In a preferable metallocene catalyst represented by the generalformula(IV), Me is zirconium, M and N are all indenyl, Y is chlorine, mis 1, and n and n' are 2.

When an organic carrier supported metallocene catalyst is used forpolymerization of olefins, an alkylaluminoxane is employed together asco-catalyst. Exemplary alkylaluminoxane is methylaluminoxane (MAO). Theco-catalyst is used in the amount of 5 to 2,000 moles per one mole ofthe metallocene catalyst. Preferably, 50 to 2,000 moles of theco-catalyst may be used.

Polymers or copolymers of olefins such as α-olefins, cycloolefins anddienvinyl monomers can be prepared using an organic carrier supportedmetallocene catalyst according to the present invention.

The invention may be better understood by reference to the followingexamples which are intended for purposes of illustration and are not tobe construed as in any way limiting the scope of the present invention,which is defined in the claims appended hereto.

EXAMPLES Example 1

Preparation of Ligand: Lithium indenylide was prepared by adding 25 g ofindene to 100 g of toluene, and reacting the resultant with 37 g ofn-butyllithium at -50° C. for 12 hours. Bisindenyldichlorosilane wasprepared by reacting the resultant with 13 g of tetrachlorosilane atroom temperature for 5 hours.

Activation of Carrier: 50 g of styrene/divinylbenzene copolymer(weightaverage molecular weight: 150,000) containing 5% by weight ofdivinylbenzene was activated with 100 g of toluene, 6 g ofn-butyllithium and 0.5 g of tetramethylethyleneamine(TMEDA) at -50° C.for 12 hours.

Synthesis of Metallocene Catalyst: The ligand was reacted with theactivated organic carrier. To 100 g of the reacting product was added500 g of tetrahydrofuran, and 86 g of n-butyllithium was added dropwise-50° C. over 8 hours. The resultant was purified by filtration, and 500g of tetrahydrofuran and 75 g of tetrachloro-zirconium were added atroom temperature for 12 hours. The metallocene catalyst of generalformula(II a) described above was obtained.

Polymerization: Propylene was polymerized using a glass reactor equippedwith a temperature controlled apparatus, a magnetic agitator and valvesfor supplying monomers and nitrogen. 300 ml of a purified toluene, 1mmole of methylaluminoxane(MAO), and 100 mg of the metallocene catalystprepared above were put into a nitrogen-substituted reactor and mixed,and propylene was added up to the reaction pressure. The polymerizationof propylene was carried out at 40° C. for 6 hours. The polymerizationwas terminated by adding 50 ml of HCl/C₂ H₅ OH solution. The resultantwas purified six times with methanol over 12 hours. The polymer wasvacuum-dried at 60° C. for 24 hours.

Copolymerization: The same reactor as in the polymerization above wasutilized. 300 ml of a purified toluene, 5 ml of MAO, and 100 mg of themetallocene catalyst prepared above were put into a nitrogen-substitutedreactor and mixed, and 13.46 mmole of propylene was added. Then ethylenewas added up to the reaction pressure of 3 atm. The copolymerization ofpropylene and ethylene was carried out at 70° C. for 6 hours. Thecopolymerization was terminated by adding 50 ml of HCl/C₂ H₅ OHsolution. The resultant was purified six times with methanol over 12hours. The copolymer was vacuum-dried at 60° C. for 24 hours.

Example 2

Example 2 was performed as in Example 1 with the exception that 16 g of1-methyltrichlorosilane was substituted for the 13 g oftetrachlorosilane of Example 1. In this Example 2, the metallocenecatalyst of general formula(II b) described above was prepared.

Example 3

Example 3 was performed as in Example 1 with the exception that 100 g ofstyrene/divinylbenzene copolymer(weight average molecular weight:150,000) containing 5% by weight of divinylbenzene was alkylated byFriedel-Crafts alkylation with monochloroisopropane andtrichloroaluminum in 500 g of toluene before the copolymer was activatedwith n-butyllithium and tetramethylethylamine(TMEDA). In this Example 3,the metallocene catalyst of general formula(I/c) described above wasprepared.

Example 4

Activation of Carrier: 50 g of styrene/divinylbenzene copolymer(weightaverage molecular weight: 150,000) containing 5% by weight ofdivinylbenzene was activated with 34 g of tetrachlorotin and 26 g ofchloroethylmethylether in 500 g of chloroform at -30° C. for 8 hours.

Preparation of Ligand and Metallocene Catalyst: 200 g of toluene and 62g of n-butyllithium were added to 47 g of diindenyl ethylene at -50° C.for 8 hours. The ligand of diindenyl ethylene was obtained. The ligandwas reacted with the activated organic carrier. To the resultant wasadded 200 g of tetrahydrofuran and tetrachlorozirconium at 60° C. for 5hours. The metallocene catalyst of general formula(IV) described abovewas prepared.

Polymerization: Propylene was polymerized using a glass reactor equippedwith a temperature controlled apparatus, a magnetic agitator and valvesfor supplying monomers and nitrogen. 300 ml of a purified toluene, 50mmole of methylaluminoxane(MAO), and 200 mg of the metallocene catalystprepared above were put into a nitrogen-substituted reactor and mixed,and propylene was added up to the reaction pressure. The polymerizationof propylene was carried out at G0° C. for 10 hours. The polymerizationwas terminated by adding 50 ml of HCl/C₂ H₅ OH solution. The resultantwas purified six times with methanol over 12 hours. The polymer wasvacuum-dried at 60° C. for 24 hours.

Copolymerization: The same reactor as in the polymerization above wasutilized. 300 ml of a purified toluene, 5 ml of MAO, and 0.09 g of themetallocene catalyst prepared above were put into a nitrogen-substitutedreactor and mixed, and 13.46 mmole of propylene was added. Then ethylenewas added up to the reaction pressure of 3 atm. The copolymerization ofpropylene and ethylene was carried out at 70° C. for 6 hours. Thecopolymerization was terminated by adding 50 ml of HCl/C₂ H₅ OHsolution. The resultant was purified six times with methanol over 12hours. The copolymer was vacuum-dried at 60° C. for 24 hours.

Comparative Examples

The following comparative Examples 1-4 are to compare with Examples 1-4in accordance with the present invention

Comparative Example 1

Catalyst: A metallocene catalyst excluding the organic carrier from thecatalyst of general formula(II a) was prepared.

Carrier Supporting: Dry silica(Davison Grade 952) was dispersed intoluene at 600° C. for 10 hours. To the dispersed solution was added themetallocene catalyst which was solved in toluene. The resultant wasmaintained to react at 70° C. for 15 hours, then washed with toluene.The silica supported metallocene catalyst was prepared.

Polymerization and Copolymerization: Polymerization and copolymerizationwere performed as in Example 1, except that the silica supportedmetallocene catalyst prepared above was employed.

Comparative Example 2

Catalyst: A metallocene catalyst excluding the organic carrier from thecatalyst of general formula(II b) was prepared.

Carrier supporting: Dry silica(Davison Grade 952) was dispersed intoluene at 600° C. for 10 hours. To the dispersed solution was added themetallocene catalyst which was solved in toluene. The resultant wasmaintained to react at 70° C. for 15 hours, then washed with toluene.The silica supported metallocene catalyst was prepared.

Polymerization and Copolymerization: Polymerization and copolymerizationwere performed as in Example 2, except that the silica supportedmetallocene catalyst prepared above was employed.

Comparative Example 3

Catalyst: A metallocene catalyst excluding the organic carrier from thecatalyst of general formula(II c) was prepared.

Carrier Supporting: Dry silica(Davison Grade 952) was dispersed intoluene at 600° C. for 10 hours. To the dispersed solution was added themetallocene catalyst which was solved in toluene. The resultant wasmaintained to react at 70° C. for 15 hours, then washed with toluene.The silica supported metallocene catalyst was prepared.

Polymerization and Copolymerization: Polymerization and copolymerizationwere performed as in Example 3, except that the silica supportedmetallocene catalyst prepared above was employed.

Comparative Example 4

Catalyst: A metallocene catalyst excluding the organic carrier from thecatalyst of general formula(IV) was prepared.

Carrier Supporting: Dry silica(Davison Grade 952) was dispersed intoluene at 600° C. for 10 hours. To the dispersed solution was added themetallocene catalyst which was solved in toluene. The resultant wasmaintained to react at 70° C. for 15 hours, then washed with toluene.The silica supported metallocene catalyst was prepared.

Polymerization and Copolymerization: Polymerization and copolymerizationwere performed as in Example 4, except that the silica supportedmetallocene catalyst prepared above was employed.

The following Table 1 sets forth the results of polymerization ofpropylene in accordance with Examples 1-3 and comparative Examples 1-3.

                  TABLE 1                                                         ______________________________________                                                Zirconium       Catalyst                                                      Content Catalyst                                                                              Activity                                                      (× 10                                                                           Yield   (Kg-PP/   MW    Tm                                            mmol-Zr/g)                                                                            (g)     mol-Zr · h)                                                                    (× 10.sup.4)                                                                  (°C.)                          ______________________________________                                        Examples                                                                              1     5.5       1.64  497     2.3   139.9                                     2     7.1       1.54  150     2.7   138                                       3     17.1      1.76  72      2.6   138.5                             Comparative                                                                           1     5.1       1.11  210     1.1   133.8                             Examples                                                                              2     4.2       0.92  60      0.8   133.5                                     3     3.8       0.78  35      0.5   132.4                             ______________________________________                                    

The following Table 2 sets forth the results of copolymerization ofethylene/propylene in accordance with Examples 1-3 and comparativeExamples 1-3.

                                      TABLE 2                                     __________________________________________________________________________            Catalyst                                                                          Co-Catalyst  Catalyst                                                     Content                                                                           Content                                                                             C2.sup.1)                                                                        C3.sup.2)                                                                         Yield                                                                             Catalyst      Tm I.I..sup.5)                             (g) (MAO, ml)                                                                           (atm)                                                                            (mmol)                                                                            (g) activity.sup.3)                                                                    MWD.sup.4)                                                                        MW   (°C.)                                                                     (%)                             __________________________________________________________________________    Examples                                                                            1 0.09                                                                              5     3  13.46                                                                             2.18                                                                              49,800                                                                             2.0 124,300                                                                            136.9                                                                            81.9                                  2 0.66                                                                              5     3   9.52                                                                             1.86                                                                              36,900                                                                             3.1 98,000                                                                             139.7                                                                            88.4                                  3 0.32                                                                              5     3  12.57                                                                             3.02                                                                              54,000                                                                             3.4 85,000                                                                             137.9                                                                            82.6                            Comparative                                                                         1 0.51                                                                              5     3   8.14                                                                             1.02                                                                              21,100                                                                             3.8 54,000                                                                             134.2                                                                            80.1                            Examples                                                                            2 0.38                                                                              5     3   9.22                                                                             1.23                                                                              18,700                                                                             4.1 39,000                                                                             133.4                                                                            82.3                                  3 0.65                                                                              5     3  10.54                                                                             0.98                                                                              12,400                                                                             4.2 48,000                                                                             132.1                                                                            82.4                            __________________________________________________________________________     Notes;                                                                        .sup.1) Pressure of ethylene                                                  .sup.2) mmoles of propylene                                                   .sup.3) KgPolymer/mol-Zr-hr                                                   .sup.4) Molecular Weight Distribution                                         .sup.5) Isotactic Index                                                  

The following Table 3 sets forth the results of polymerization ofpropylene in accordance with Example 4 and Comparative Example 4.

                  TABLE 3                                                         ______________________________________                                        Zirconium              Catalyst                                               Content        Catalyst                                                                              Activity                                               (× 10.sup.3                                                                            Yield   (Kg-PP/   MW    Tm                                     mmol-Zr/g)     (g)     mol-Zr · h)                                                                    (× 10.sup.4)                                                                  (°C.)                           ______________________________________                                        Examples 4                                                                            8.4        1.33    650     2.5   138.4                                Comparative                                                                           6.1        0.87    330     1.8   136.7                                Examples 4                                                                    ______________________________________                                    

The following Table 4 sets forth the results of copolymerization ofethylene/propylene in accordance with Example 4 and Comparative Example4.

                                      TABLE 4                                     __________________________________________________________________________    Catalyst  Co-Catalyst  Catalyst                                               Content   Content                                                                             C2.sup.1)                                                                        C3.sup.2)                                                                         yield                                                                             Catalyst     Tm I.I..sup.5)                        (g)       (MAO, ml)                                                                           (atm)                                                                            (mmol)                                                                            (g) activity.sup.3)                                                                    MWD.sup.4)                                                                        MW  (°C.)                                                                     (%)                                __________________________________________________________________________    Examples 4                                                                          0.69                                                                              5     3  24.5                                                                              2.89                                                                              43,000                                                                             2.8 93,000                                                                            138.4                                                                            83.5                               Comparative                                                                         0.69                                                                              5     3  25  2.05                                                                              38,000                                                                             3.2 72,000                                                                            136.1                                                                            82.2                               Examples 4                                                                    __________________________________________________________________________     Notes;                                                                        .sup.1) Pressure of ethylene                                                  .sup.2) mmoles of propylene                                                   .sup.3) KgPolymer/mol-Zr-hr                                                   .sup.4) Molecular Weight Distribution                                         .sup.5) Isotactic Index                                                  

In Tables 1-4, metal content, catalyst activity and melting point(Tin)were measured as the following methods.

Metal Content: 0.5 g of metallocene catalyst was dissolved in nitricacid, and the resultant was diluted with water. A test solution wasobtained. The zirconium content was measured using an InductivelyCoupled Plasma Spectrophotometer(ICP).

Catalyst Activity: The catalyst activity was obtained inKg-Polymer/mol-Zr-atm by measuring weight of polymer prepared bypolymerization.

Melting Point: The melting point was obtained using Du Pont 2000System(DSC) under nitrogen atmosphere with an aluminum pan of 6 mg ofpolymer. The temperature rate was 10° C./min.

Further modifications of the invention will be apparent to those skilledin the art and all such modifications are deemed to be with the scope ofthe invention as defined in the following claims.

What is claimed is:
 1. An organic carrier supported metallocene catalystfor olefin polymerization represented by the general formula (IIa):##STR5## wherein M and N are selected from the group consisting ofcyclopentadienyl, indenyl, fluorenyl, alkyl-substituted indenyl, andalkyl-substituted fluorenyl and are the same or different from eachother, Me is a transition metal of Group IVb of the Periodic Table orLanthanides, and Y is a halogen, a lower alkyl of C₁ -C₆ or phenoxy,prepared by a process comprising:preparing a ligand complex of a siliconcompound having at least one halogen, an alkyl group and acycloalkanedienyl group, represented by the general formula (I):##STR6## wherein A is a halogen or a lower alkyl off C₁ -C₆, X is ahalogen, or a phenoxy, and M and N are selected from the groupconsisting of cyclopentadienyl, indenyl, fluorenyl, alkyl-substitutedindenyl, and alkyl-substituted fluorenyl, and are the same or differentfrom each other; activating an organic carrier with a strong basecontaining a metal atom selected from the group consisting of Li, Na, Kand Mg, wherein said organic carrier is a styrene polymer; reacting saidactivated organic carrier with said ligand complex of a silicon compoundin a base so that said ligand is supported to said activated organiccarrier; and reacting said organic carrier supported ligand with acompound of a transition metal of Group IVb of the Periodic Table orLanthanides of Atomic Number 58-71, and further comprising an activator.2. An organic carrier supported metallocene catalyst for olefinpolymerization represented by the general formula (IV): ##STR7## whereinM and N are selected from the group consisting of cyclopentadienyl,indenyl, fluorenyl, alkyl-substituted indenyl, and alkyl-substitutedfluorenyl, and are the same or different from each other, Me is atransition metal of Group IVb of the Periodic Table, or Lanthanides, andY is a halogen, a lower alkyl of C₁ -C₆ or a or phenoxy, m is an integerof 1-3, n is an integer of 2-4, and n' is an integer, prepared by aprocess comprising:preparing a ligand complex of an alkylene bondedcycloalkanediene represented by the general formula (III): ##STR8##wherein M and N are selected from the group consisting ofcyclopentadienyl, indenyl, fluorenyl, alkyl-substituted indenyl, andalkyl-substituted fluorenyl and are the same or different from eachother; activating an organic carrier with a halogenated alkyl ether in aLewis acid, wherein said organic carrier is a styrene polymer; reactingsaid activated organic carrier with said ligand complex of an alkylenebonded cycloalkanediene in a strong base so that said ligand issupported to said activated organic carrier; and reacting said organiccarrier supported ligand with a compound of a transition metal of GroupIVb of the Periodic Table or Lanthanides of Atomic Number 58-71, andfurther comprising an activator.